"Export to PDF" vs "Print to PDF": What's Actually Different
Both produce a PDF from the same document, but they go through different pipelines internally, and the results aren't always equivalent — one preserves more of the original document than the other.
"Export to PDF" (or "Save as PDF")
This uses the source application's own PDF export engine, which has direct access to the document's real structure — actual paragraphs, actual table objects, actual embedded fonts and hyperlinks. A Word document exported to PDF this way keeps working hyperlinks, a proper document outline/bookmarks if headings are structured correctly, and searchable, selectable text drawn from the real characters, not an image of them.
"Print to PDF"
This routes the document through the operating system's print pipeline, using a virtual "printer" that captures print output as a PDF instead of physical paper. Because it goes through the same path as printing to an actual printer, it generally reproduces visual layout accurately — but it can lose things that only exist for on-screen or interactive use: hyperlinks sometimes don't survive, form fields can become flat/uneditable, and document structure (bookmarks, tagged headings) is often stripped since a physical printer never needed that information.
When it actually matters
For a simple document you just need to look right, either method usually works fine. It matters when the PDF needs to do more than just display: if you need working hyperlinks, an editable form, proper accessibility tagging for screen readers, or a navigable bookmark outline, use the source application's direct "Export to PDF" rather than printing to PDF — the difference in output isn't visual, so it's easy to not notice until someone tries to click a link that no longer works.